JP2010177030A - Surface treating agent of lithium based composite oxide, surface treating liquid of lithium based composite oxide, electrolyte for lithium-ion secondary battery, positive electrode active material for surface-treated lithium-ion secondary battery and method of manufacturing the same, negative electrode active material for surface-treated lithium-ion secondary battery and method of manufacturing the same, and lithium-ion secondary battery and method of manufacturing the same - Google Patents
Surface treating agent of lithium based composite oxide, surface treating liquid of lithium based composite oxide, electrolyte for lithium-ion secondary battery, positive electrode active material for surface-treated lithium-ion secondary battery and method of manufacturing the same, negative electrode active material for surface-treated lithium-ion secondary battery and method of manufacturing the same, and lithium-ion secondary battery and method of manufacturing the same Download PDFInfo
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Abstract
Description
本発明は、リチウムイオン二次電池の正極活物質用、負極活物質用等のリチウム系複合酸化物の表面を処理するための表面処理剤、それを含有する表面処理液及び電解液、それにより表面処理されたリチウムイオン二次電池用正極活物質又は負極活物質、それらの製造方法、それを用いるリチウムイオン二次電池及びその製造方法に関する。 The present invention relates to a surface treatment agent for treating the surface of a lithium-based composite oxide for a positive electrode active material, a negative electrode active material, etc. of a lithium ion secondary battery, a surface treatment liquid and an electrolyte containing the same, and thereby The present invention relates to a surface-treated positive electrode active material or negative electrode active material for a lithium ion secondary battery, a production method thereof, a lithium ion secondary battery using the same, and a production method thereof.
近年、家庭電器においてポータブル化、コードレス化が急速に進むに従い、ラップトップ型パソコン、携帯電話、ビデオカメラ等の小型電子機器の電源としてリチウムイオン二次電池が実用化されている。このリチウムイオン二次電池については、リチウム系複合酸化物を正極活物質とするリチウムイオン二次電池に関する研究開発が活発に進められており、これまで多くの提案がなされている。 In recent years, as home appliances have become portable and cordless, lithium ion secondary batteries have been put to practical use as power sources for small electronic devices such as laptop computers, mobile phones, and video cameras. With regard to this lithium ion secondary battery, research and development on lithium ion secondary batteries using a lithium-based composite oxide as a positive electrode active material has been actively promoted, and many proposals have been made so far.
例えば、特開平０４−５６０６４号公報（特許文献１）には、リチウムイオン二次電池の正極活物質として残留Ｌｉ２ＣＯ３が１０質量％以下であるＬｉＣｏＯ２を用いることが開示されている。また、特開平０２−４０８６１号公報（特許文献２）には、リチウム二次電池用の正極活物質としてＬｉb Ｎｉ2-b Ｏ2 及びＬｉＮｉ1-d Ｃｏd Ｏ2 （但し、０．８４≦ｂ≦１．２２、０．０９≦ｄ≦０．５）を用いることが開示されている。また、特開平０７−３３５２６１号公報（特許文献３）には、リチウム二次電池用の負極活物質としてＬｉ４／３Ｔｉ５／３Ｏ４を用いることが開示されている。 For example, Japanese Laid-Open Patent Publication No. 04-56064 (Patent Document 1) discloses using LiCoO 2 having a residual Li 2 CO 3 content of 10% by mass or less as a positive electrode active material of a lithium ion secondary battery. Further, Japanese Unexamined 02-40861 (Patent Document 2), Li b Ni 2- b O 2 and LiNi as a positive electrode active material for lithium secondary batteries 1-d Co d O 2 (where 0.84 ≦ b ≦ 1.22, 0.09 ≦ d ≦ 0.5) is disclosed. Japanese Unexamined Patent Publication No. 07-335261 (Patent Document 3) discloses the use of Li 4/3 Ti 5/3 O 4 as a negative electrode active material for a lithium secondary battery.
しかしながら、リチウム系複合酸化物は、リチウム源として、水酸化リチウムや炭酸リチウム等のアルカリを用いて製造されるために、得られるリチウム系複合酸化物中には、アルカリが残存してしまう。 However, since the lithium-based composite oxide is produced using an alkali such as lithium hydroxide or lithium carbonate as a lithium source, the alkali remains in the obtained lithium-based composite oxide.
そして、リチウム系複合酸化物中の残存アルカリは、絶縁性の化合物であるため放電容量を低下させるとされている。また、リチウム系複合酸化物表面において強アルカリ成分として働くため電解液が分解され易いという問題点を有している。 The remaining alkali in the lithium-based composite oxide is an insulating compound, and thus is said to reduce the discharge capacity. Moreover, since it acts as a strong alkali component on the surface of the lithium-based composite oxide, there is a problem that the electrolytic solution is easily decomposed.
そのため、従来のリチウム系複合酸化物を正極活物質とするリチウム二次電池には、充放電を繰り返すと、放電容量が低下するという問題、急速充放電したときの充放電特性が悪いという問題、電解質の分解によりガスが発生するという問題、保存安定性、特に、高温での保存安定性が十分でないという問題があった。 Therefore, the conventional lithium secondary battery using a lithium-based composite oxide as a positive electrode active material has a problem that the discharge capacity decreases when charging and discharging are repeated, a problem that charging / discharging characteristics are poor when rapidly charging and discharging, There are problems that gas is generated due to decomposition of the electrolyte, and storage stability, particularly storage stability at high temperatures is not sufficient.
従って、本発明の課題は、リチウム系複合酸化物を正極活物質又は負極活物質として用いるリチウムイオン二次電池であって、サイクル特性、急速充放電特性及び保存安定性に優れるリチウムイオン二次電池を提供することにある。 Accordingly, an object of the present invention is a lithium ion secondary battery that uses a lithium-based composite oxide as a positive electrode active material or a negative electrode active material, and is excellent in cycle characteristics, rapid charge / discharge characteristics, and storage stability. Is to provide.
本発明者らは、上記従来技術における課題を解決すべく、鋭意研究を重ねた結果、リチウムイオン二次電池用の正極活物質又は負極活物質として用いられるリチウム系複合酸化物に、特定の多価のカチオンと、リチウムイオン二次電池の電解質用リチウム塩のアニオンと、からなる化合物を接触させると、該化合物が、リチウム系複合酸化物の残存アルカリと容易に反応して、該残存アルカリが、アルカリ性の低いアルカリ化合物に変換されるため、残存アルカリによる電解質の分解を防ぐことができ、また、生じた低アルカリ性のアルカリ化合物により、リチウム系複合酸化物の表面が被覆されるため、リチウム系複合酸化物による電解質の分解を防ぐことができ、さらに、該化合物由来のリチウムイオン二次電池の電解質用リチウム塩のアニオンと残存アルカリ由来のリチウムイオンにより生じる化合物は、リチウム塩電解質として活用され得る。そのため、リチウムイオン二次電池のサイクル特性、急速充放電特性及び保存安定性が向上することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-described problems in the prior art, the present inventors have found that a lithium-based composite oxide used as a positive electrode active material or a negative electrode active material for a lithium ion secondary battery has a specific When a compound consisting of a valent cation and an anion of a lithium salt for electrolyte of a lithium ion secondary battery is contacted, the compound easily reacts with the remaining alkali of the lithium-based composite oxide, and the remaining alkali Since it is converted into an alkaline compound having low alkalinity, it is possible to prevent decomposition of the electrolyte due to residual alkali, and since the surface of the lithium-based composite oxide is covered with the generated low alkaline alkaline compound, the lithium-based The decomposition of the electrolyte by the composite oxide can be prevented, and further, the lithium salt for the electrolyte of the lithium ion secondary battery derived from the compound can be prevented. Compounds resulting from the the remaining alkali from the lithium ion anion can be used as a lithium salt electrolyte. Therefore, it has been found that the cycle characteristics, rapid charge / discharge characteristics and storage stability of the lithium ion secondary battery are improved, and the present invention has been completed.
すなわち、本発明（１）は、下記一般式（１）：
Ｍ１ （ａ）Ｘ（ｂ） （１）
（式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ａｌ、Ｇｅ、Ｔｉ及びＺｒのうちの１種又は２種以上の多価のカチオンである。Ｘは、リチウムイオン二次電池の電解質用リチウム塩のアニオンである。ａ＞０であり、ｂ＞０である。）
で表わされる化合物であることを特徴とするリチウム系複合酸化物の表面処理剤を提供するものである。
That is, the present invention (1) includes the following general formula (1):
M 1 (a) X (b) (1)
(In the formula, M 1 is one or more polyvalent cations of Mg, Ca, Sr, Ba, Zn, Al, Ge, Ti, and Zr. X is a lithium ion secondary battery. An anion of the lithium salt for electrolytes, a> 0 and b> 0.)
A surface treatment agent for a lithium-based composite oxide, which is a compound represented by the formula:
また、本発明（２）は、本発明（１）のリチウム系複合酸化物の表面処理剤を含有することを特徴とするリチウム系複合酸化物の表面処理液を提供するものである。 In addition, the present invention (2) provides a surface treatment liquid for a lithium-based composite oxide characterized by containing the surface treatment agent for a lithium-based composite oxide of the present invention (1).
また、本発明（３）は、本発明（１）のリチウム系複合酸化物の表面処理剤を含有することを特徴とするリチウムイオン二次電池用電解液を提供するものである。 Moreover, this invention (3) provides the electrolyte solution for lithium ion secondary batteries characterized by including the surface treating agent of lithium type complex oxide of this invention (1).
また、本発明（４）は、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を、本発明（１）のリチウム系複合酸化物の表面処理剤で、表面処理して得られたものであることを特徴とする表面処理リチウムイオン二次電池用正極活物質を提供するものである。 Moreover, this invention (4) was obtained by surface-treating the lithium composite oxide for positive electrode active materials of a lithium ion secondary battery with the surface treatment agent for the lithium composite oxide of the present invention (1). The present invention provides a positive electrode active material for a surface-treated lithium ion secondary battery.
また、本発明（５）は、リチウムイオン二次電池の負極活物質用リチウム系複合酸化物を、本発明（１）のリチウム系複合酸化物の表面処理剤で、表面処理して得られたものであることを特徴とする表面処理リチウムイオン二次電池用負極活物質を提供するものである。 In addition, the present invention (5) was obtained by surface-treating a lithium-based composite oxide for a negative electrode active material of a lithium ion secondary battery with the surface treatment agent for a lithium-based composite oxide of the present invention (1). The present invention provides a negative electrode active material for a surface-treated lithium ion secondary battery.
また、本発明（６）は、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を、本発明（２）のリチウム系複合酸化物の表面処理液、又は本発明（３）のリチウムイオン二次電池用電解液と、接触させることを特徴とする表面処理リチウムイオン二次電池用正極活物質の製造方法を提供するものである。 Further, the present invention (6) includes a lithium-based composite oxide for a positive electrode active material of a lithium ion secondary battery, a surface treatment solution for the lithium-based composite oxide of the present invention (2), or the lithium of the present invention (3). The present invention provides a method for producing a positive electrode active material for a surface-treated lithium ion secondary battery, which is brought into contact with an electrolytic solution for an ion secondary battery.
また、本発明（７）は、リチウムイオン二次電池の負極活物質用リチウム系複合酸化物を、本発明（２）のリチウム系複合酸化物の表面処理液、又は本発明（３）のリチウムイオン二次電池用電解液と、接触させることを特徴とする表面処理リチウムイオン二次電池用負極活物質の製造方法を提供するものである。 Further, the present invention (7) includes a lithium-based composite oxide for a negative electrode active material of a lithium ion secondary battery, a surface treatment solution for the lithium-based composite oxide of the present invention (2), or the lithium of the present invention (3). The present invention provides a method for producing a negative electrode active material for a surface-treated lithium ion secondary battery, which is brought into contact with an electrolytic solution for an ion secondary battery.
また、本発明（８）は、正極活物質が、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を、本発明（１）のリチウム系複合酸化物の表面処理剤で表面処理して得た表面処理リチウムイオン二次電池用正極活物質を含有することを特徴とするリチウムイオン二次電池を提供するものである。 In the present invention (8), the positive electrode active material is obtained by surface-treating the lithium composite oxide for the positive electrode active material of the lithium ion secondary battery with the surface treatment agent for the lithium composite oxide of the present invention (1). A lithium ion secondary battery comprising the positive electrode active material for a surface-treated lithium ion secondary battery obtained as described above is provided.
また、本発明（９）負極活物質が、リチウムイオン二次電池の負極活物質用リチウム系複合酸化物を、本発明（１）のリチウム系複合酸化物の表面処理剤で表面処理して得た表面処理リチウムイオン二次電池用負極活物質を含有することを特徴とするリチウムイオン二次電池を提供するものである。 Moreover, this invention (9) negative electrode active material obtained by surface-treating the lithium type complex oxide for negative electrode active materials of a lithium ion secondary battery with the surface treatment agent of the lithium type complex oxide of this invention (1). The present invention provides a lithium ion secondary battery comprising a negative electrode active material for a surface-treated lithium ion secondary battery.
また、本発明（１０）は、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を含有する正極活物質と負極活物質とを、あるいは、正極活物質とリチウムイオン二次電池の負極活物質用リチウム系複合酸化物を含有する負極活物質とを、あるいは、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を含有する正極活物質とリチウムイオン二次電池の負極活物質用リチウム系複合酸化物を含有する負極活物質とを、リチウムイオン二次電池の容器の所定の位置に配置し、次いで、該リチウムイオン二次電池の容器に、本発明（３）のリチウムイオン二次電池用電解液を注入して、該正極活物質及び該負極活物質と、該リチウムイオン二次電池用電解液とを接触させることを特徴とするリチウムイオン二次電池の製造方法を提供するものである。 Further, the present invention (10) provides a positive electrode active material and a negative electrode active material containing a lithium-based composite oxide for a positive electrode active material of a lithium ion secondary battery, or a positive electrode active material and a negative electrode of a lithium ion secondary battery. A negative electrode active material containing a lithium-based composite oxide for an active material, or a positive electrode active material containing a lithium-based composite oxide for a positive electrode active material of a lithium ion secondary battery and a negative electrode active material of a lithium ion secondary battery And a negative electrode active material containing a lithium-based composite oxide for use in a predetermined position of a container of a lithium ion secondary battery, and then the lithium ion of the present invention (3) in the container of the lithium ion secondary battery A method for producing a lithium ion secondary battery, comprising injecting an electrolyte solution for a secondary battery, and bringing the positive electrode active material and the negative electrode active material into contact with the electrolyte solution for a lithium ion secondary battery It is intended to provide.
本発明によれば、リチウム系複合酸化物を正極活物質又は負極活物質として用いるリチウムイオン二次電池であって、サイクル特性、急速充放電特性及び保存安定性に優れるリチウムイオン二次電池を提供することができる。 According to the present invention, there is provided a lithium ion secondary battery that uses a lithium-based composite oxide as a positive electrode active material or a negative electrode active material, and is excellent in cycle characteristics, rapid charge / discharge characteristics, and storage stability. can do.
本発明のリチウム系複合酸化物の表面処理剤（以下、本発明の表面処理剤（ａ）とも記載する。）は、下記一般式（１）：
Ｍ１ （ａ）Ｘ（ｂ） （１）
（式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ａｌ、Ｇｅ、Ｔｉ及びＺｒのうちの１種又は２種以上の多価のカチオンである。Ｘは、リチウムイオン二次電池の電解質用リチウム塩のアニオンである。ａ＞０であり、ｂ＞０である。）
で表わされる化合物であるリチウム系複合酸化物の表面処理剤である。
The surface treatment agent of the lithium-based composite oxide of the present invention (hereinafter also referred to as the surface treatment agent (a) of the present invention) is represented by the following general formula (1)
M 1 (a) X (b) (1)
(In the formula, M 1 is one or more polyvalent cations of Mg, Ca, Sr, Ba, Zn, Al, Ge, Ti, and Zr. X is a lithium ion secondary battery. An anion of the lithium salt for electrolytes, a> 0 and b> 0.)
A surface treatment agent for a lithium-based composite oxide, which is a compound represented by the formula:
本発明の表面処理剤（ａ）は、リチウムイオン二次電池の活物質、すなわち、正極活物質又は負極活物質として用いられるリチウム系複合酸化物の表面を処理するための表面処理剤である。 The surface treatment agent (a) of the present invention is a surface treatment agent for treating the surface of an active material of a lithium ion secondary battery, that is, a lithium composite oxide used as a positive electrode active material or a negative electrode active material.
そして、本発明の表面処理剤（ａ）は、前記一般式（１）で表わされる化合物である。前記一般式（１）中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ａｌ、Ｇｅ、Ｔｉ及びＺｒのうちの１種又は２種以上のカチオンであり、且つ、２価以上の多価カチオンである。これらのうち、Ｍ１としては、Ｍｇ、Ｃａ、Ｓｒ、Ｚｎ、Ａｌ、Ｔｉ及びＺｒが、サイクル特性、急速充放電特性及び保存安定性が高くなる点で好ましい。 And the surface treating agent (a) of this invention is a compound represented by the said General formula (1). In the general formula (1), M 1 is one or two or more cations of Mg, Ca, Sr, Ba, Zn, Al, Ge, Ti, and Zr, and a divalent or higher cation. It is a valent cation. Among these, M 1, Mg, Ca, Sr , Zn, Al, Ti and Zr, the cycle characteristics, preferable because rapid charge and discharge characteristics and storage stability is increased.
前記一般式（１）中、Ｘは、リチウムイオン二次電池の電解質用リチウム塩のアニオンであり、サイクル特性、急速充放電特性及び保存安定性が高くなる点で、Ｂ（Ｃ２Ｏ４）２、ＣｌＯ４、ＰＦ６、ＢＦ４、Ｎ（ＳＯ２ＣＦ３）２、ＣＦ２ＨＣＯＯ、ＰＦ４（Ｃ２Ｏ４）２、Ｂ１２Ｆ１２、Ｂ（ＣＮ）４、Ｎ（ＳＯ２Ｆ）２、ＣＦ３ＣＯＣＨＣＯＣＦ３、ＣＨ３ＣＯＣＨＣＯＣＦ３、が好ましい。これらは、１種単独又は２種以上の組み合わせでもよい。なお、リチウムイオン二次電池の電解質として用いられているリチウム塩には、アニオンとして、塩化物イオン、臭素化物イオン又はヨウ化物イオンを有するものもあるが、本発明に係るリチウムイオン二次電池の電解質用リチウム塩のアニオンとしては、Ｃｌ−、Ｂｒ−及びＩ−は除かれる。本発明において、リチウムイオン二次電池の電解質用リチウム塩とは、リチウムイオン二次電池の電解質として用いられているリチウム塩のことであり、例えば、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＢ１０Ｃｌ１０、ＬｉＰＦ６、ＬｉＣＦ３ＳＯ３、ＬｉＣＦ３ＣＯ２、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＡｌＣｌ４、ＣＨ３ＳＯ３Ｌｉ、ＣＦ３ＳＯ３Ｌｉ、（ＣＦ３ＳＯ２）２ＮＬｉ、クロロボランリチウム、低級脂肪族カルボン酸リチウム、四フェニルホウ酸リチウム、イミド類等が挙げられる。 In the general formula (1), X is an anion of a lithium salt for an electrolyte of a lithium ion secondary battery, and B (C 2 O 4 ) is improved in terms of cycle characteristics, rapid charge / discharge characteristics, and storage stability. 2 , ClO 4 , PF 6 , BF 4 , N (SO 2 CF 3 ) 2 , CF 2 HCOO, PF 4 (C 2 O 4 ) 2 , B 12 F 12 , B (CN) 4 , N (SO 2 F ) 2 , CF 3 COCHCOCF 3 , and CH 3 COCHCOCF 3 . These may be used alone or in combination of two or more. In addition, some lithium salts used as electrolytes of lithium ion secondary batteries have chloride ions, bromide ions or iodide ions as anions, but the lithium ion secondary batteries according to the present invention As the anion of the electrolyte lithium salt, Cl − , Br − and I − are excluded. In the present invention, the lithium salt for an electrolyte of a lithium ion secondary battery is a lithium salt used as an electrolyte of a lithium ion secondary battery. For example, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, chloroborane lithium, lower aliphatic carboxyl Lithium acid, lithium tetraphenylborate, imides and the like can be mentioned.
なお、本発明において、リチウムイオン二次電池の電解質用リチウム塩のアニオンとは、リチウムイオン二次電池の電解質用リチウム塩として用いることがきるリチウム塩のアニオンという意味であり、本発明の表面処理剤を用いて表面処理した活物質用リチウム系複合酸化物が用いられるリチウムイオン二次電池で、実際に電解質として用いられるリチウム塩と、同じアニオンに限定されるものではない。例えば、ＸがＢ（Ｃ２Ｏ４）２である本発明の表面処理剤（ａ）で、正極活物質用リチウム複合酸化物を処理し、次いで、表面処理された正極活物質用リチウム複合酸化物を、正極活物質として用いてリチウムイオン二次電池を製造する際に、電解質として用いられるリチウム塩は、ＸがＢ（Ｃ２Ｏ４）２であるリチウム塩に限定されず、ＸがＣｌＯ４であるリチウム塩であってもよい。 In the present invention, the anion of the lithium salt for electrolyte of the lithium ion secondary battery means an anion of lithium salt that can be used as the lithium salt for electrolyte of the lithium ion secondary battery, and the surface treatment of the present invention. The lithium ion secondary battery using the active material lithium composite oxide surface-treated with an agent is not limited to the same anion as the lithium salt actually used as the electrolyte. For example, with the surface treating agent (a) of the present invention in which X is B (C 2 O 4 ) 2 , the lithium composite oxide for positive electrode active material is treated, and then the surface-treated lithium composite oxide for positive electrode active material is treated. When a lithium ion secondary battery is manufactured using a product as a positive electrode active material, a lithium salt used as an electrolyte is not limited to a lithium salt where X is B (C 2 O 4 ) 2 , and X is ClO 4 may be a lithium salt.
前記一般式（１）中、ａ＞０であり、ｂ＞０であり、ａ及びｂは、Ｍ及びＸの価数により異なる。 In the general formula (1), a> 0, b> 0, and a and b differ depending on the valence of M and X.
本発明の表面処理剤（ａ）は、前記一般式（１）で表わされる化合物のうちの１種単独又は２種以上の組み合わせであってもよい。 The surface treating agent (a) of the present invention may be a single compound or a combination of two or more compounds among the compounds represented by the general formula (1).
本発明の表面処理剤（ａ）により表面処理されるリチウムイオン二次電池の正極活物質用リチウム系複合酸化物（以下、本発明に係る正極活物質用リチウム系複合酸化物（ｂ１））は、リチウムイオン二次電池の正極活物質として用いられるリチウム系複合酸化物であれば、特に制限されないが、サイクル特性、急速充放電特性及び保存安定性が高くなる点で、下記一般式（３）：
Ｌｉ（ｃ）Ｎｉ（ｄ）Ｃｏ（ｅ）Ｍｎ（ｆ）Ａｌ（ｇ）Ｏ２ （３）
（式中、０．８≦ｃ≦１．２、０≦ｄ≦１、０≦ｅ≦１、０≦ｆ≦１、０≦ｇ≦０．１、ｄ＋ｅ＋ｆ＋ｇ＝１である。）
で表わされるリチウム系複合酸化物が、特に好ましい。
The lithium-based composite oxide for a positive electrode active material of a lithium ion secondary battery surface-treated with the surface treatment agent (a) of the present invention (hereinafter, the lithium-based composite oxide for positive electrode active material (b1) according to the present invention) is The lithium-based composite oxide used as the positive electrode active material of the lithium ion secondary battery is not particularly limited, but the following general formula (3) is provided in that the cycle characteristics, rapid charge / discharge characteristics, and storage stability are enhanced. :
Li (c) Ni (d) Co (e) Mn (f) Al (g) O 2 (3)
(In the formula, 0.8 ≦ c ≦ 1.2, 0 ≦ d ≦ 1, 0 ≦ e ≦ 1, 0 ≦ f ≦ 1, 0 ≦ g ≦ 0.1, d + e + f + g = 1)
A lithium-based composite oxide represented by
また、本発明の表面処理剤（ａ）により表面処理されるリチウムイオン二次電池の負極活物質用リチウム系複合酸化物（以下、本発明に係る負極活物質用リチウム系複合酸化物（ｂ２））は、リチウムイオン二次電池の負極活物質として用いられるリチウム系複合酸化物であれば、特に制限されないが、サイクル特性、急速充放電特性及び保存安定性が高くなる点で、チタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２）、リチウムサイトの一部が他の１種以上の金属元素で置換されたチタン酸リチウム、チタンサイトの一部が他の１種以上の金属元素で置換されたチタン酸リチウム、又はリチウムサイトの一部が他の１種以上の金属元素で置換され且つチタンサイトの一部が他の１種以上の金属元素で置換されたチタン酸リチウムが、特に好ましい。ここで、チタン酸リチウムのリチウム元素又はチタン元素と置換される上記他の金属元素は、Ｌｉを除くアルカリ金属、アルカリ土類金属、Ａｌ、Ｓｉ、Ｐ及び遷移金属である。 Further, the lithium-based composite oxide for a negative electrode active material of a lithium ion secondary battery surface-treated with the surface treatment agent (a) of the present invention (hereinafter, the lithium-based composite oxide for negative electrode active material (b2) according to the present invention) ) Is not particularly limited as long as it is a lithium-based composite oxide used as a negative electrode active material for a lithium ion secondary battery, but lithium titanate (in terms of improving cycle characteristics, rapid charge / discharge characteristics, and storage stability) Li 4 Ti 5 O 12 ), lithium titanate in which part of the lithium site is substituted with one or more other metal elements, titanic acid in which part of the titanium site is substituted with one or more other metal elements Lithium or lithium titanate in which part of the lithium site is replaced with one or more other metal elements and part of the titanium site is replaced with one or more other metal elements is particularly preferred. . Here, the above-mentioned other metal elements substituted for lithium element or titanium element of lithium titanate are alkali metals, alkaline earth metals, Al, Si, P and transition metals except Li.
なお、以下、本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）及び本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）を総称して、リチウムイオン二次電池の正極又は負極用の活物質として用いられるリチウム系複合酸化物を、本発明に係る活物質用リチウム系複合酸化物（ｂ）とも記載する。 Hereinafter, the lithium-based composite oxide for positive electrode active material (b1) according to the present invention and the lithium-based composite oxide for negative electrode active material (b2) according to the present invention are collectively referred to as a positive electrode of a lithium ion secondary battery or The lithium composite oxide used as the negative electrode active material is also referred to as the active material lithium composite oxide (b) according to the present invention.
リチウムイオン二次電池の正極活物質用のリチウム系複合酸化物及びリチウムイオン二次電池の負極活物質用のリチウム系複合酸化物は、水酸化リチウム、炭酸リチウム等のリチウム系のアルカリを原料に用いて製造されるため、これらのリチウム系複合酸化物中には、原料の由来のリチウム系のアルカリが残存している。本発明では、このようなリチウム系複合酸化物の表面に残存しているリチウム系アルカリに、本発明の表面処理剤（ａ）を反応させることにより、リチウム系複合酸化物を表面処理することができる。 The lithium-based composite oxide for the positive electrode active material of the lithium ion secondary battery and the lithium-based composite oxide for the negative electrode active material of the lithium ion secondary battery are made from lithium-based alkali such as lithium hydroxide and lithium carbonate. Therefore, lithium-based alkalis derived from the raw materials remain in these lithium-based composite oxides. In the present invention, the lithium-based composite oxide can be surface-treated by reacting the surface-treating agent (a) of the present invention with the lithium-based alkali remaining on the surface of the lithium-based composite oxide. it can.
本発明の表面処理剤（ａ）により、本発明に係る活物質用リチウム系複合酸化物（ｂ）を表面処理する方法としては、本発明の表面処理剤（ａ）を含有する表面処理液と、本発明に係る活物質用リチウム系複合酸化物（ｂ）を接触させる方法が挙げられる。 As a method for surface-treating the lithium composite oxide for active material (b) according to the present invention with the surface treatment agent (a) of the present invention, a surface treatment liquid containing the surface treatment agent (a) of the present invention and And a method of contacting the lithium-based composite oxide for active material (b) according to the present invention.
このような表面処理に用いられる表面処理液、すなわち、本発明のリチウム系複合酸化物の表面処理液（以下、本発明の表面処理液（ｃ）とも記載する。）は、本発明の表面処理剤（ａ）を含有する。 The surface treatment liquid used for such surface treatment, that is, the surface treatment liquid of the lithium composite oxide of the present invention (hereinafter also referred to as the surface treatment liquid (c) of the present invention) is the surface treatment of the present invention. Contains agent (a).
本発明の表面処理液（ｃ）では、本発明の表面処理剤（ａ）が、溶剤に分散又は溶解されている。本発明の表面処理液（ｃ）に係る溶剤としては、本発明の表面処理剤（ａ）及び本発明に係る活物質用リチウム系複合酸化物（ｂ）に対して不活性なものであればよく、例えば、アルコール、アセトン、プロピレンカーボネート、ジメチルカーボネート／エチレンカーボネート混合溶媒等が挙げられる。 In the surface treatment liquid (c) of the present invention, the surface treatment agent (a) of the present invention is dispersed or dissolved in a solvent. As the solvent for the surface treatment liquid (c) of the present invention, any solvent that is inactive with respect to the surface treatment agent (a) of the present invention and the lithium composite oxide for active material (b) of the present invention may be used. For example, alcohol, acetone, propylene carbonate, dimethyl carbonate / ethylene carbonate mixed solvent and the like can be mentioned.
本発明の表面処理液（ｃ）中、本発明の表面処理剤（ａ）の含有量は、好ましくは０．０１〜１０質量％、特に好ましくは０．１〜５質量％である。本発明の表面処理液（ｃ）中の本発明の表面処理剤（ａ）の含有量が上記範囲にあることにより、効率的にリチウム系複合酸化物の表面を処理できると共に未反応処理剤の残留を抑制できる。 In the surface treatment liquid (c) of the present invention, the content of the surface treatment agent (a) of the present invention is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 5% by mass. When the content of the surface treatment agent (a) of the present invention in the surface treatment liquid (c) of the present invention is in the above range, the surface of the lithium composite oxide can be efficiently treated and an unreacted treatment agent Residual can be suppressed.
本発明の表面処理剤（ａ）により、本発明に係る活物質用リチウム系複合酸化物（ｂ）を表面処理する方法としては、他には、本発明の表面処理剤（ａ）を含有する電解液と、本発明に係る活物質用リチウム系複合酸化物（ｂ）を接触させる方法が挙げられる。 In addition, the surface treatment agent (a) of the present invention includes the surface treatment agent (a) of the present invention as a method for surface-treating the lithium composite oxide for active material (b) of the present invention. Examples include a method of bringing the electrolytic solution into contact with the lithium-based composite oxide for active material (b) according to the present invention.
このような表面処理に用いられる電解液、すなわち、本発明のリチウムイオン二次電池用電解液（以下、本発明の電解液（ｄ）とも記載する。）は、本発明の表面処理剤（ａ）を含有する。 The electrolytic solution used for such surface treatment, that is, the electrolytic solution for a lithium ion secondary battery of the present invention (hereinafter also referred to as the electrolytic solution (d) of the present invention) is the surface treating agent (a ).
本発明の電解液（ｄ）では、本発明の表面処理剤（ａ）が、リチウムイオン二次電池用の電解液に分散又は溶解されている。本発明の電解液（ｄ）に係るリチウムイオン二次電池用の電解液としては、通常、リチウムイオン二次電池用の電解液として用いられるものであればよく、例えば、ジメチルカーボネート、エチルメチルカーボネート、エチレンカーボネート、プロピレンカーボネート、γブチロラクトンやこれらのフッ素化溶媒等の非水溶媒を適宜混合したものに、例えば、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＢ（Ｃ２Ｏ４）２、ＬｉＣｌＯ４等の電解質を、溶解させた電解液が挙げられる。 In the electrolytic solution (d) of the present invention, the surface treating agent (a) of the present invention is dispersed or dissolved in an electrolytic solution for a lithium ion secondary battery. The electrolyte solution for the lithium ion secondary battery according to the electrolyte solution (d) of the present invention may be any one that is usually used as an electrolyte solution for a lithium ion secondary battery, such as dimethyl carbonate, ethyl methyl carbonate. For example, LiPF 6 , LiBF 4 , LiN (SO 2 CF 3 ) 2 , LiB (C 2 O 4 ) can be appropriately mixed with nonaqueous solvents such as ethylene carbonate, propylene carbonate, γ-butyrolactone, and fluorinated solvents thereof. ) 2 , and an electrolyte solution in which an electrolyte such as LiClO 4 is dissolved.
本発明の電解液（ｄ）中、本発明の表面処理剤（ａ）の含有量は、好ましくは０．００１〜５質量％、特に好ましくは０．０５〜２質量％である。本発明の電解液（ｄ）中の本発明の表面処理剤（ａ）の含有量が上記範囲にあることにより、効率的にリチウム系複合酸化物の表面を処理することができると共に未反応処理剤による性能低下を抑制することができる。 In the electrolytic solution (d) of the present invention, the content of the surface treatment agent (a) of the present invention is preferably 0.001 to 5% by mass, particularly preferably 0.05 to 2% by mass. When the content of the surface treating agent (a) of the present invention in the electrolytic solution (d) of the present invention is in the above range, the surface of the lithium composite oxide can be efficiently treated and unreacted treatment Performance degradation due to the agent can be suppressed.
本発明の電解液（ｄ）を用いて、本発明の表面処理剤（ａ）により、本発明に係る活物質用リチウム系複合酸化物（ｂ）の表面処理を行う方法の形態例としては、例えば、リチウムイオン二次電池を組み立てる際に、先ず、正極、負極、セパレータ等の材料を電池内の所定の位置に配置し、次いで、電池内に本発明の電解液（ｄ）を注入することにより、電池内で、本発明の電解液（ｄ）と本発明に係る活物質用リチウム系複合酸化物（ｂ）を接触させる方法が挙げられる。そして、本発明の電解液（ｄ）を注入後、電池を密閉して、リチウムイオン二次電池を製造することができる。 As an embodiment of the method for performing the surface treatment of the lithium-based composite oxide for active material (b) according to the present invention with the surface treatment agent (a) of the present invention using the electrolytic solution (d) of the present invention, For example, when assembling a lithium ion secondary battery, first, materials such as a positive electrode, a negative electrode, and a separator are arranged at predetermined positions in the battery, and then the electrolyte solution (d) of the present invention is injected into the battery. In the battery, a method of bringing the electrolytic solution (d) of the present invention into contact with the lithium composite oxide for active material (b) according to the present invention can be mentioned. And after inject | pouring the electrolyte solution (d) of this invention, a battery can be sealed and a lithium ion secondary battery can be manufactured.
また、上記で、電池内に本発明の電解液（ｄ）を注入して、本発明の電解液（ｄ）と本発明に係る活物質用リチウム系複合酸化物（ｂ）との接触を十分に行った後、密閉せずに、必要に応じて注入した電解液を電池外に排出し、次いで、電池内に、新たな本発明の電解液（ｄ）又はそれ以外のリチウムイオン二次電池用の電解液を注入して、電池を密閉し、リチウムイオン二次電池を製造することもできる。 In addition, in the above, the electrolytic solution (d) of the present invention is injected into the battery, and sufficient contact between the electrolytic solution (d) of the present invention and the lithium-based composite oxide for active material (b) according to the present invention is ensured. Then, the electrolytic solution injected as needed is discharged out of the battery without sealing, and then the new electrolytic solution (d) of the present invention or other lithium ion secondary battery is put in the battery. A lithium ion secondary battery can also be manufactured by injecting an electrolyte solution for sealing and sealing the battery.
本発明の表面処理剤（ａ）により、本発明に係る活物質用リチウム複合酸化物（ｂ）の表面処理を行う方法としては、他には、リチウムイオン二次電池を組み立てる際に、予め、本発明の表面処理剤（ａ）を、正極、負極又はセパレータ中に存在させておき、次いで、電池内に電解液を注入して、正極、負極又はセパレータに、電解液を接触させることにより、電池内で、本発明の表面処理剤（ａ）を電解液に溶解させ、そして、本発明の表面処理剤（ａ）が溶解した電解液と正極又は負極の本発明に係る活物質用リチウム系複合酸化物（ｂ）を接触させる方法が挙げられる。ここで、本発明の表面処理剤（ａ）を正極又は負極中に存在させる方法としては、例えば、固体の本発明の表面処理剤（ａ）と固体の正極材又は負極材とを撹拌混合する方法が挙げられる。また、本発明に係る活物質用リチウム複合酸化物（ｂ）の表面処理を行う方法としては、他には、正極ペースト又は負極ペーストを調製するための溶媒に、本発明の表面処理剤（ａ）を溶解又は分散させておき、得られた溶液又は分散液を用いたペーストにより電極シートを作製する方法、本発明の表面処理液（ｃ）と固体の正極材又は負極材とを接触させた後電極シートを作製する方法、正極又は負極の電極シートを作製した後、得られた電極シート上の正極材又は負極材と本発明の表面処理液（ｃ）とを接触させる方法等が挙げられ、また、本発明の表面処理剤（ａ）をセパレータ中に存在させる方法としては、例えば、本発明の表面処理剤を溶解又は分散したセパレータを製膜する方法、セパレータを本発明の表面処理液（ｃ）に浸漬し乾燥させて表面処理剤を担持させる方法等が挙げられる。 As a method of performing the surface treatment of the lithium composite oxide for active material (b) according to the present invention with the surface treatment agent (a) of the present invention, in addition, when assembling a lithium ion secondary battery, By causing the surface treatment agent (a) of the present invention to exist in the positive electrode, the negative electrode or the separator, and then injecting the electrolytic solution into the battery and bringing the electrolytic solution into contact with the positive electrode, the negative electrode or the separator, In a battery, the surface treatment agent (a) of the present invention is dissolved in an electrolytic solution, and the electrolytic solution in which the surface treatment agent (a) of the present invention is dissolved and a positive electrode or a negative electrode for an active material according to the present invention The method of making a complex oxide (b) contact is mentioned. Here, as a method for causing the surface treatment agent (a) of the present invention to exist in the positive electrode or the negative electrode, for example, the solid surface treatment agent (a) of the present invention and the solid positive electrode material or negative electrode material are mixed by stirring. A method is mentioned. In addition, as a method for performing the surface treatment of the lithium composite oxide for active material (b) according to the present invention, the surface treatment agent (a) of the present invention may be used in a solvent for preparing a positive electrode paste or a negative electrode paste. ) Is dissolved or dispersed, and the surface treatment liquid (c) of the present invention and the solid positive electrode material or negative electrode material are brought into contact with each other, a method for producing an electrode sheet with the obtained solution or paste using the dispersion liquid Examples thereof include a method of preparing a post electrode sheet, a method of contacting a positive electrode material or a negative electrode material on the obtained electrode sheet and the surface treatment liquid (c) of the present invention after preparing a positive electrode or negative electrode sheet. In addition, examples of the method for causing the surface treatment agent (a) of the present invention to exist in the separator include, for example, a method of forming a separator in which the surface treatment agent of the present invention is dissolved or dispersed, and the separator as a surface treatment liquid of the present invention. Immersion in (c) Method in which dried by carrying a surface treatment agent.
このように、本発明の表面処理剤（ａ）により、本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）を表面処理することにより、表面処理されたリチウムイオン二次電池用正極活物質が得られる。 In this way, the surface treatment agent (a) of the present invention is used to surface-treat the lithium-based composite oxide (b1) for a positive electrode active material according to the present invention, so that the surface-treated positive electrode active for a lithium ion secondary battery is treated. A substance is obtained.
本発明の表面処理リチウムイオン二次電池用正極活物質（以下、本発明の表面処理正極活物質（ｅ）とも記載する。）は、本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）を、本発明の表面処理剤（ａ）で表面処理して得られたものである。 The positive electrode active material for a surface-treated lithium ion secondary battery of the present invention (hereinafter also referred to as the surface-treated positive electrode active material (e) of the present invention) is a lithium-based composite oxide (b1) for a positive electrode active material according to the present invention. ) Is surface-treated with the surface treating agent (a) of the present invention.
本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）中の残存アルカリ量は、好ましくは０．０２〜３質量％、特に好ましくは０．０５〜２質量％である。本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）中の残存アルカリ量が０．０２質量％より小さいと、表面処理によるサイクル特性、急速充放電特性及び保存安定性改善効果が小さくなり易くなり、３質量％より大きいと表面処理による被覆量が大きくなり過ぎることにより急速充放電特性が低くなり易くなる。正極活物質用リチウム系複合酸化物（ｂ１）中の残存アルカリ量が上記範囲にあることにより、サイクル特性、急速充放電特性及び保存安定性を高くすることができる。 The residual alkali amount in the lithium composite oxide (b1) for the positive electrode active material according to the present invention is preferably 0.02 to 3% by mass, particularly preferably 0.05 to 2% by mass. When the residual alkali amount in the lithium-based composite oxide (b1) for the positive electrode active material according to the present invention is smaller than 0.02% by mass, the cycle characteristics, rapid charge / discharge characteristics and storage stability improving effect due to the surface treatment are reduced. If it exceeds 3% by mass, the amount of coating by the surface treatment becomes too large, so that the rapid charge / discharge characteristics tend to be lowered. When the residual alkali amount in the lithium-based composite oxide (b1) for the positive electrode active material is in the above range, cycle characteristics, rapid charge / discharge characteristics, and storage stability can be enhanced.
また、本発明の表面処理剤（ａ）により、本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）を表面処理することにより、表面処理されたリチウムイオン二次電池用負極活物質が得られる。 Moreover, the surface-treated negative electrode active material for a lithium ion secondary battery is obtained by surface-treating the lithium-based composite oxide for negative electrode active material (b2) according to the present invention with the surface treatment agent (a) of the present invention. can get.
本発明の表面処理リチウムイオン二次電池用負極活物質（以下、本発明の表面処理負極活物質（ｆ）とも記載する。）は、本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）を、本発明の表面処理剤（ａ）で表面処理して得られたものである。 The negative electrode active material for a surface-treated lithium ion secondary battery of the present invention (hereinafter also referred to as the surface-treated negative electrode active material (f) of the present invention) is a lithium-based composite oxide (b2) for a negative electrode active material according to the present invention. ) Is surface-treated with the surface treating agent (a) of the present invention.
本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）中の残存アルカリ量は、好ましくは０．０２〜３質量％、特に好ましくは０．０５〜２質量％である。本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）中の残存アルカリ量が０．０２質量％より小さいと表面処理によるサイクル特性、急速充放電特性及び保存安定性改善効果が小さくなり易くなり、３質量％より大きいと表面処理による被覆量が大きくなり過ぎることにより急速充放電特性が低くなり易くなる。負極活物質用リチウム系複合酸化物（ｂ２）中の残存アルカリ量が上記範囲にあることにより、サイクル特性、急速充放電特性及び保存安定性を高くすることができる。 The residual alkali amount in the lithium-based composite oxide for negative electrode active material (b2) according to the present invention is preferably 0.02 to 3% by mass, particularly preferably 0.05 to 2% by mass. When the residual alkali amount in the lithium-based composite oxide (b2) for the negative electrode active material according to the present invention is smaller than 0.02% by mass, the cycle characteristics, rapid charge / discharge characteristics and storage stability improvement effect due to surface treatment tend to be small. When the content is larger than 3% by mass, the amount of coating by the surface treatment becomes too large, and the rapid charge / discharge characteristics tend to be lowered. When the residual alkali amount in the lithium-based composite oxide (b2) for the negative electrode active material is in the above range, cycle characteristics, rapid charge / discharge characteristics, and storage stability can be enhanced.
なお、本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）及び本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）中の残存アルカリ量は、これらのリチウム系複合酸化物の製造原料として用いるリチウム系のアルカリの量を選択することにより、調節することができる。そして、本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）及び本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）中の残存アルカリ量を調節することにより、本発明の表面処理剤（ａ）よる表面処理量を調節することができる。 The residual alkali amount in the lithium-based composite oxide (b1) for the positive electrode active material according to the present invention and the lithium-based composite oxide (b2) for the negative electrode active material according to the present invention is the amount of these lithium-based composite oxides. It can be adjusted by selecting the amount of the lithium-based alkali used as the production raw material. And the surface of this invention is adjusted by adjusting the residual alkali amount in the lithium type complex oxide (b1) for positive electrode active materials which concerns on this invention, and the lithium type complex oxide for negative electrode active materials which concerns on this invention (b2). The amount of surface treatment by the treatment agent (a) can be adjusted.
また、本発明の表面処理リチウムイオン二次電池用正極活物質の製造方法は、本発明に係る正極活物質用リチウム系複合酸化物（ｂ１）を、本発明の表面処理液（ｃ）、又は本発明の電解液（ｄ）と、接触させることにより、本発明の表面処理正極活物質（ｅ）を得る表面処理リチウムイオン二次電池用正極活物質の製造方法である。また、本発明の表面処理リチウムイオン二次電池用負極活物質の製造方法は、本発明に係る負極活物質用リチウム系複合酸化物（ｂ２）を、本発明の表面処理液（ｃ）、又は本発明の電解液（ｄ）と、接触させることにより、本発明の表面処理負極活物質（ｆ）を得る表面処理リチウムイオン二次電池用負極活物質の製造方法である。 Moreover, the manufacturing method of the positive electrode active material for surface treatment lithium ion secondary batteries of this invention makes the surface treatment liquid (c) of this invention for the lithium type complex oxide (b1) for positive electrode active materials which concerns on this invention, or It is a manufacturing method of the positive electrode active material for surface treatment lithium ion secondary batteries which obtains the surface treatment positive electrode active material (e) of this invention by making it contact with the electrolyte solution (d) of this invention. Moreover, the manufacturing method of the negative electrode active material for surface treatment lithium ion secondary batteries of this invention makes the surface treatment liquid (c) of this invention for the lithium type complex oxide (b2) for negative electrode active materials which concerns on this invention, or It is a manufacturing method of the negative electrode active material for surface treatment lithium ion secondary batteries which obtains the surface treatment negative electrode active material (f) of this invention by making it contact with the electrolyte solution (d) of this invention.
本発明のリチウムイオン二次電池は、正極活物質が、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を、本発明の表面処理剤（ａ）で表面処理して得た本発明の表面処理リチウムイオン二次電池用正極活物質（ｅ）を含有するリチウムイオン二次電池である。 The lithium ion secondary battery of the present invention is obtained by subjecting a lithium-based composite oxide for a positive electrode active material of a lithium ion secondary battery to surface treatment with the surface treatment agent (a) of the present invention. It is a lithium ion secondary battery containing the positive electrode active material (e) for surface treatment lithium ion secondary batteries.
また、本発明のリチウムイオン二次電池は、負極活物質が、リチウムイオン二次電池の負極活物質用リチウム系複合酸化物を、本発明の表面処理剤（ａ）で表面処理して得た本発明の表面処理リチウムイオン二次電池用負極活物質（ｆ）を含有するリチウムイオン二次電池である。 Moreover, the lithium ion secondary battery of the present invention was obtained by subjecting a lithium-based composite oxide for a negative electrode active material of a lithium ion secondary battery to a surface treatment with the surface treatment agent (a) of the present invention. It is a lithium ion secondary battery containing the negative electrode active material (f) for surface treatment lithium ion secondary batteries of this invention.
また、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を含有する正極活物質と負極活物質とを、あるいは、正極活物質とリチウムイオン二次電池の負極活物質用リチウム系複合酸化物を含有する負極活物質とを、あるいは、リチウムイオン二次電池の正極活物質用リチウム系複合酸化物を含有する正極活物質とリチウムイオン二次電池の負極活物質用リチウム系複合酸化物を含有する負極活物質とを、リチウムイオン二次電池の容器の所定の位置に配置し、次いで、該リチウムイオン二次電池の容器に、本発明の電解液（ｄ）を注入して、該正極活物質及び該負極活物質と、本発明の電解液（ｄ）とを接触させるリチウムイオン二次電池の製造方法である。 Also, a positive electrode active material and a negative electrode active material containing a lithium composite oxide for a positive electrode active material of a lithium ion secondary battery, or a lithium composite oxide for a negative electrode active material of a positive electrode active material and a lithium ion secondary battery A negative active material containing a product, or a positive active material containing a lithium composite oxide for a positive active material of a lithium ion secondary battery and a lithium composite oxide for a negative active material of a lithium ion secondary battery The negative electrode active material contained is disposed at a predetermined position of a container of a lithium ion secondary battery, and then the electrolyte solution (d) of the present invention is injected into the container of the lithium ion secondary battery, It is a manufacturing method of the lithium ion secondary battery which makes an active material and this negative electrode active material contact the electrolyte solution (d) of this invention.
リチウム系複合酸化物の表面には、未反応の原料由来のリチウム系アルカリが残存しており、このリチウム系アルカリは、水酸化リチウム、炭酸リチウム等の強アルカリ性のリチウム塩である。これに対して、本発明の表面処理剤（ａ）は、２価以上の多価カチオンを有しているので、リチウム系アルカリと反応することにより、リチウムイオンと本発明の表面処理剤（ａ）に由来する多価カチオンとがイオン交換し、多価のアルカリと、Ｌｉ（ｎ）Ｘ塩（ｎはＸの価数により異なる。）とが生成する。そして、イオン交換によって生じる多価のアルカリは、リチウム系アルカリに比べると、アルカリ性が低いため、正極活物質又は負極活物質中の残存アルカリによる悪影響を少なくすることができる。加えて、イオン交換によって生じるＬｉ（ｎ）Ｘ塩は、リチウムイオン二次電池の電解質用のリチウム塩なので、リチウムイオン二次電池に対して、悪影響を与えることはない。 An unreacted raw material-derived lithium-based alkali remains on the surface of the lithium-based composite oxide, and this lithium-based alkali is a strong alkaline lithium salt such as lithium hydroxide or lithium carbonate. On the other hand, since the surface treatment agent (a) of the present invention has a divalent or higher polyvalent cation, the surface treatment agent (a) of the present invention (a) reacts with a lithium-based alkali. ) Are ion-exchanged with each other to produce a polyvalent alkali and a Li (n) X salt (n is different depending on the valence of X). And since the polyvalent alkali produced by ion exchange has a lower alkalinity than a lithium-based alkali, adverse effects due to residual alkali in the positive electrode active material or the negative electrode active material can be reduced. In addition, since the Li (n) X salt generated by ion exchange is a lithium salt for an electrolyte of a lithium ion secondary battery, it does not adversely affect the lithium ion secondary battery.
更に、本発明の表面処理剤とリチウム系アルカリとの反応によりリチウム系複合酸化物の表面に生じる多価のアルカリは、そのまま存在するか、又は酸化物になる。そして、このような多価のアルカリ及びその酸化物は、リチウム系複合酸化物に比べ、非水溶媒の分解に対する活性が低いため、リチウム系複合酸化物の表面は、活性が低い物質で被覆されることになる。そのため、リチウム系複合酸化物の高過ぎる表面活性を、低く抑えることができ、非水電解液の分解を抑制することができる。 Furthermore, the polyvalent alkali generated on the surface of the lithium composite oxide by the reaction between the surface treatment agent of the present invention and the lithium alkali is present as it is or becomes an oxide. Such polyvalent alkalis and oxides thereof are less active against decomposition of non-aqueous solvents than lithium-based composite oxides, so the surface of lithium-based composite oxides is coated with a less active substance. Will be. Therefore, the surface activity of the lithium composite oxide that is too high can be kept low, and the decomposition of the nonaqueous electrolytic solution can be suppressed.
また、従来より行われてきた水洗等によるアルカリ成分の除去方法では水分の残存等による電池特性の低下や保存特性の低下が生じてしまうという問題点があった。また、酸化物やリン酸塩等によるリチウム系複合酸化物の被覆方法では、リチウム系複合酸化物に、固体の酸化物やリン酸塩の微粒子を表面に付着させることによって被覆を行うため、表面に均一に被覆することが困難であり、添加量も多く、アルカリ成分が残存するため保存特性を改善することができないなどの問題点があった。またリチウム系複合酸化物をアルコキシドのアルコール溶液などに浸漬し、次いで焼成することによりリチウム系複合酸化物表面に酸化物を析出させる方法では、工程が複雑で生産性が悪く、アルカリ成分が残存するため保存特性を改善することが出来ない等の問題点があった。それに対し、本発明の表面処理剤（ａ）で表面処理する場合は、本発明の表面処理剤（ａ）が強アルカリ性のアルカリ成分と選択的に反応するため、極めて少量の本発明の表面処理剤（ａ）と残存アルカリ成分との反応物で被覆して、活物質表面のアルカリ性を低下させることができる。また、表面処理後の焼成や乾燥といった工程が不要であるため生産性に優れ、被覆ムラや被覆量が多過ぎることによる容量低下や表面抵抗の低下ということは起こり難い。 In addition, the conventional method for removing an alkali component by washing or the like has a problem in that battery characteristics and storage characteristics are deteriorated due to moisture remaining. In addition, in the method of coating a lithium-based composite oxide with an oxide, phosphate, or the like, the surface of the lithium-based composite oxide is coated by attaching solid oxide or phosphate fine particles to the surface. In other words, it is difficult to coat uniformly, the amount added is large, and the alkali component remains, so that the storage characteristics cannot be improved. Moreover, in the method of depositing an oxide on the surface of a lithium-based composite oxide by immersing the lithium-based composite oxide in an alcohol solution of an alkoxide and then firing, the process is complicated, the productivity is poor, and an alkali component remains. Therefore, there are problems such as inability to improve storage characteristics. On the other hand, when the surface treatment with the surface treatment agent (a) of the present invention is carried out, the surface treatment agent (a) of the present invention selectively reacts with a strongly alkaline alkaline component, so that a very small amount of the surface treatment of the present invention is performed. It can coat | cover with the reaction material of an agent (a) and a residual alkali component, and can reduce the alkalinity of the active material surface. Further, since steps such as baking and drying after the surface treatment are unnecessary, the productivity is excellent, and it is difficult to cause a decrease in capacity or a decrease in surface resistance due to coating unevenness or excessive coating amount.
これらのことから、本発明の表面処理剤（ａ）により、リチウムイオン二次電池の活物質用リチウム系複合酸化物を表面処理し、得られる表面処理リチウムイオン二次電池の活物質用リチウム系複合酸化物を、活物質として用いることにより、リチウムイオン二次電池のサイクル特性、急速充放電特性及び保存安定性を高くすることができる。 From these facts, the surface treatment agent (a) of the present invention surface-treats the lithium-based composite oxide for the active material of the lithium ion secondary battery, and the resulting lithium-based active material for the surface-treated lithium ion secondary battery. By using the composite oxide as an active material, the cycle characteristics, rapid charge / discharge characteristics, and storage stability of the lithium ion secondary battery can be enhanced.
本発明の表面処理剤（ａ）を製造する方法としては、特に制限されず、例えば、Ｍ１の炭酸塩、水酸化物、炭酸水素塩、硝酸塩等のＭ１の塩と、前記一般式（１）中のＸをアニオンとする酸と、を反応させる方法や、Ｍ１の炭酸塩、水酸化物、炭酸水素塩、硝酸塩等のＭ１の塩と、前記一般式（１）中のＸをアニオンとする酸を生成する化合物の組み合わせと、を反応させる方法が挙げられる。また、これらの反応は、液相反応であっても、固相反応であってもよい。 As a method for producing a surface treatment agent (a) of the present invention is not particularly limited, for example, carbonates of M 1, hydroxides, hydrogen carbonates, and salts of M 1 of the nitrates, the general formula ( and acid X-1) in the anion, and a method of reacting a carbonate salt of M 1, hydroxides, hydrogen carbonates, and salts of M 1 of nitrates, X in the general formula (1) And a combination of compounds that generate an acid having an anion as the anion. In addition, these reactions may be liquid phase reactions or solid phase reactions.
更に具体的には、例えば、Ｍｇ（Ｂ（Ｃ２Ｏ４）２）２を製造する場合、（ｉ）Ｍ１の塩として、水酸化マグネシウムを用い、前記一般式（１）中のＸをアニオンとする酸を生成する化合物の組み合わせとして、無水蓚酸及びホウ酸を用い、水酸化マグネシウムと、無水蓚酸及びホウ酸とを、混合し、得られた混合物を不活性雰囲気下で焼成することにより、固相で反応を行い、Ｍｇ（Ｂ（Ｃ２Ｏ４）２）２を得る方法や、（ｉｉ）Ｍ１の塩として、炭酸マグネシウムを用い、前記一般式（１）中のＸをアニオンとする酸を生成する化合物の組み合わせとして、蓚酸２水和物及びホウ酸を用い、反応溶媒となる水中に、炭酸マグネシウムと、蓚酸２水和物及びホウ酸とを添加して、液相中で反応を行い、Ｍｇ（Ｂ（Ｃ２Ｏ４）２）２を得る方法が挙げられる。 More specifically, for example, when producing Mg (B (C 2 O 4 ) 2 ) 2 , (i) magnesium hydroxide is used as the salt of M 1 , and X in the general formula (1) is By combining succinic anhydride and boric acid as a combination of compounds that generate an anion acid, magnesium hydroxide, succinic anhydride and boric acid are mixed, and the resulting mixture is baked in an inert atmosphere. , By reacting in a solid phase to obtain Mg (B (C 2 O 4 ) 2 ) 2 , or (ii) using magnesium carbonate as a salt of M 1 , X in the general formula (1) is anion As a combination of compounds that produce acid, oxalic acid dihydrate and boric acid are used, and magnesium carbonate, oxalic acid dihydrate and boric acid are added to water as a reaction solvent, and in the liquid phase in carrying out the reaction, Mg (B (C 2 O 4) ) Method and the like to obtain a 2.
なお、本発明の表面処理剤（ａ）を製造するための製造条件、例えば、反応温度、反応時間、撹拌方式等は、適宜選択される。 In addition, the manufacturing conditions for manufacturing the surface treating agent (a) of the present invention, for example, the reaction temperature, the reaction time, the stirring method, and the like are appropriately selected.
以下、本発明を実施例により詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
＜表面処理剤：Ｍｇ（Ｂ（Ｃ２Ｏ４）２）２の調製＞
（実施例１）
無水蓚酸を１２．３ｇ、ホウ酸を４．２ｇと水酸化マグネシウム２．０ｇを量りとり、乳鉢で粉砕しながら十分混合した。このとき、Ｍｇ／Ｂ／Ｃ２Ｏ４＝１／２／４（モル比）である。得られた混合物を窒素雰囲気下で２５０℃で５時間焼成し、白色粉末を得た。この白色粉末のＸＲＤ測定（Ｂｒｕｋｅｒ社製 Ｄ８ ＡＤＶＡＮＣＥ）を行ったところ、得られたＸＲＤチャートからは、原料化合物のピークは観察されなかった。また、この白色粉末のＦＴ−ＩＲ測定（ＪＡＳＣＯ社製 ＦＴ／ＩＲ−４３０）を行ったところ、Ｍｇ（Ｂ（Ｃ２Ｏ４）２）２であることが確認された。
<Preparation of surface treatment agent: Mg (B (C 2 O 4 ) 2 ) 2 >
Example 1
12.3 g of succinic anhydride, 4.2 g of boric acid and 2.0 g of magnesium hydroxide were weighed and mixed well while being pulverized in a mortar. At this time, it is Mg / B / C 2 O 4 = 1/2/4 (molar ratio). The obtained mixture was baked at 250 ° C. for 5 hours under a nitrogen atmosphere to obtain a white powder. When XRD measurement (D8 ADVANCE manufactured by Bruker) of this white powder was performed, no peak of the raw material compound was observed from the obtained XRD chart. When it was FT-IR measurement of the white powder (JASCO Corporation FT / IR-430), it was confirmed Mg (B (C 2 O 4 ) 2) 2.
＜Ｌｉ４Ｔｉ５Ｏ１２負極の調製＞
（参考例１）
二酸化チタンと炭酸リチウムをＬｉ／Ｔｉモル比がＬｉ／Ｔｉ＝４／５となるように混合し、大気雰囲気中で７５０℃で１０時間焼成した。得られた白色粉末を粉砕分級しＸＲＤ測定を行ったところ、Ｌｉ４Ｔｉ５Ｏ１２であることを確認した。
<Preparation of Li 4 Ti 5 O 12 negative electrode>
(Reference Example 1)
Titanium dioxide and lithium carbonate were mixed so that the Li / Ti molar ratio was Li / Ti = 4/5, and fired at 750 ° C. for 10 hours in an air atmosphere. When the obtained white powder was pulverized and classified and subjected to XRD measurement, it was confirmed to be Li 4 Ti 5 O 12 .
＜電解液の調製＞
（実施例２）
１０ｍｌのエチレンカーボネート／ジメチルカーボネート＝１／１（体積比）の混合溶媒に１ＭのＬｉＰＦ６を溶解させた電解液Ｅ０（キシダ化学社製、リチウムバッテリーグレード）に、実施例１で調製したＭｇ（Ｂ（Ｃ２Ｏ４）２）２ ０．０５ｇを溶解させて、電解液Ｅ１を調製した。
<Preparation of electrolyte>
(Example 2)
Mg prepared in Example 1 in an electrolytic solution E0 (made by Kishida Chemical Co., Ltd., lithium battery grade) in which 1 M LiPF 6 was dissolved in a mixed solvent of 10 ml of ethylene carbonate / dimethyl carbonate = 1/1 (volume ratio). B (C 2 O 4 ) 2 ) 2 0.05 g was dissolved to prepare an electrolytic solution E1.
（実施例３）
１０ｍｌのエチレンカーボネート／ジメチルカーボネート＝１／１（体積比）の混合溶媒に１ＭのＬｉＣｌＯ４を溶解させた電解液Ｅ２（キシダ化学社製、リチウムバッテリーグレード）に、市販のＣａ（ＣｌＯ４）２（キシダ化学社製）０．０５ｇを溶解させて、電解液Ｅ３を調製した。
(Example 3)
Commercially available Ca (ClO 4 ) 2 in an electrolytic solution E2 (Kishida Chemical Co., Ltd., lithium battery grade) in which 1M LiClO 4 is dissolved in a mixed solvent of 10 ml of ethylene carbonate / dimethyl carbonate = 1/1 (volume ratio). 0.05 g (Kishida Chemical Co., Ltd.) was dissolved to prepare an electrolytic solution E3.
＜表面処理液の調製＞
（実施例４）
市販のエチレンカーボネート（キシダ化学社製、リチウムバッテリーグレード）と市販のジメチルカーボネート（キシダ化学社製、リチウムバッテリーグレード）を体積比で１：１の割合で混合した。当該混合液１０ｍｌに、実施例１で調製したＭｇ（Ｂ（Ｃ２Ｏ４）２）２を０．０５ｇ溶解させて、表面処理液Ｓ１を調製した。
<Preparation of surface treatment solution>
Example 4
Commercially available ethylene carbonate (manufactured by Kishida Chemical Co., Ltd., lithium battery grade) and commercially available dimethyl carbonate (manufactured by Kishida Chemical Co., Ltd., lithium battery grade) were mixed at a volume ratio of 1: 1. 0.05 g of Mg (B (C 2 O 4 ) 2 ) 2 prepared in Example 1 was dissolved in 10 ml of the mixed solution to prepare a surface treatment solution S1.
＜正極板の作製＞
正極活物質としてＬｉＮｉ０．８Ｍｎ０．１Ｃｏ０．１Ｏ２（日本化学工業社製、セルシードＮ（登録商標）、残留アルカリ量１．８質量％）９１質量％、炭素粉末（ＴＩＭＣＡＬ社製、ＳＵＰＥＲ Ｐ）６質量％、ポリフッ化ビニリデン３質量％を混合して正極材とし、これをＮ−メチル−２−ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストをアルミ箔に塗布したのち乾燥、プレスして直径１５ｍｍの円盤に打ち抜いて正極板Ｃ１を得た。
<Preparation of positive electrode plate>
LiNi 0.8 Mn 0.1 Co 0.1 O 2 (manufactured by Nippon Chemical Industry Co., Ltd., Cellseed N (registered trademark), residual alkali amount 1.8% by mass) 91% by mass, carbon powder (TIMCAL) Manufactured by SUPER P) and 6% by mass of polyvinylidene fluoride were mixed to obtain a positive electrode material, which was dispersed in N-methyl-2-pyrrolidinone to prepare a kneaded paste. The kneaded paste was applied to an aluminum foil, dried, pressed and punched into a disk having a diameter of 15 mm to obtain a positive plate C1.
＜正極板の作製＞
正極活物質としてＬｉＣｏＯ２（日本化学工業社製、セルシードＣ２０（登録商標）、残留アルカリ量０．０４質量％）９１質量％、炭素粉末（ＴＩＭＣＡＬ社製、ＳＵＰＥＲ Ｐ）６質量％、ポリフッ化ビニリデン３質量％を混合して正極材とし、これをＮ−メチル−２−ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストをアルミ箔に塗布したのち乾燥、プレスして直径１５ｍｍの円盤に打ち抜いて正極板Ｃ２を得た。
<Preparation of positive electrode plate>
As a positive electrode active material, LiCoO 2 (manufactured by Nippon Chemical Industry Co., Ltd., Cellseed C20 (registered trademark), residual alkali amount 0.04% by mass) 91% by mass, carbon powder (manufactured by TIMCAL, SUPER P) 6% by mass, polyvinylidene fluoride 3% by mass was mixed to obtain a positive electrode material, which was dispersed in N-methyl-2-pyrrolidinone to prepare a kneaded paste. The kneaded paste was applied to an aluminum foil, dried, pressed and punched into a disk having a diameter of 15 mm to obtain a positive plate C2.
正極活物質としてＬｉＣｏＯ２（日本化学工業社製、セルシードＣ２０（登録商標）、残留アルカリ量０．０４質量％）を水洗したＬｉＣｏＯ２（残留アルカリ量０．０１質量％）９１質量％、炭素粉末（ＴＩＭＣＡＬ社製、ＳＵＰＥＲ Ｐ）６質量％、ポリフッ化ビニリデン３質量％を混合して正極材とし、これをＮ−メチル−２−ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストをアルミ箔に塗布したのち乾燥、プレスして直径１５ｍｍの円盤に打ち抜いて正極板Ｃ３を得た。 LiCoO 2 as a positive electrode active material (Nippon Chemical Industrial Co., Cellseed C20 (registered trademark), the residual alkali content 0.04 wt%) LiCoO 2 (residual alkali content 0.01 wt%) was washed with water 91% by mass, carbon powder (SUPAL P, manufactured by TIMCAL) 6% by mass and 3% by mass of polyvinylidene fluoride were mixed to prepare a positive electrode material, which was dispersed in N-methyl-2-pyrrolidinone to prepare a kneaded paste. The kneaded paste was applied to an aluminum foil, dried, pressed and punched into a disk having a diameter of 15 mm to obtain a positive plate C3.
＜負極板の作製＞
負極活物質として黒鉛（昭和電工社製、ＳＣＭＧ（登録商標））９１質量％、ポリフッ化ビニリデン９質量％を混合して負極材とし、これをＮ−メチル−２−ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストを銅箔に塗布したのち乾燥、プレスして直径１５ｍｍの円盤に打ち抜いて負極板Ａ１を得た。
<Preparation of negative electrode plate>
As a negative electrode active material, graphite (SCMG (registered trademark), 91% by mass) and 9% by mass of polyvinylidene fluoride are mixed to make a negative electrode material, which is dispersed in N-methyl-2-pyrrolidinone and kneaded paste Was prepared. The kneaded paste was applied to a copper foil, dried, pressed and punched into a disk with a diameter of 15 mm to obtain a negative electrode plate A1.
＜負極板の作製＞
負極活物質として参考例１で調製したＬｉ４Ｔｉ５Ｏ１２７０質量％、炭素粉末（ＴＩＭＣＡＬ社製、ＳＵＰＥＲ Ｐ）１５質量％、ポリフッ化ビニリデン１５質量％を混合して負極材とし、これをＮ−メチル−２−ピロリジノンに分散させて混練ペーストを調製した。該混練ペーストを銅箔に塗布したのち乾燥、プレスして直径１５ｍｍの円盤に打ち抜いて負極板Ａ２を得た。
<Preparation of negative electrode plate>
As a negative electrode active material, 70% by mass of Li 4 Ti 5 O 12 prepared in Reference Example 1, 15% by mass of carbon powder (SUPER P, manufactured by TIMCAL), and 15% by mass of polyvinylidene fluoride were mixed to obtain a negative electrode material. A kneaded paste was prepared by dispersing in N-methyl-2-pyrrolidinone. The kneaded paste was applied to a copper foil, dried, pressed and punched into a disk with a diameter of 15 mm to obtain a negative electrode plate A2.
＜表面処理正極板の作製＞
（実施例５）
実施例４で調製した表面処理液Ｓ１を１０ｍｌのＰＦＡ樹脂製容器に入れ、その中に正極板Ｃ１を完全に浸漬した。１時間後、正極板Ｃ１を取り出し、ジメチルカーボネートで洗浄、乾燥させて表面処理正極板Ｃ４を得た。
<Production of surface-treated positive electrode plate>
(Example 5)
The surface treatment liquid S1 prepared in Example 4 was placed in a 10 ml PFA resin container, and the positive electrode plate C1 was completely immersed therein. After 1 hour, the positive electrode plate C1 was taken out, washed with dimethyl carbonate, and dried to obtain a surface-treated positive electrode plate C4.
＜リチウムイオン二次電池の作製＞
（実施例６〜８、比較例１〜２、参考例２）
表１に示す正極板、負極板及び電解液を用いて、セパレータ、スペーサー、バネ等の各部材を使用して、２０３２タイプコインセル型リチウムイオン二次電池を作製した。
<Production of lithium ion secondary battery>
(Examples 6-8, Comparative Examples 1-2, Reference Example 2)
Using the positive electrode plate, the negative electrode plate, and the electrolytic solution shown in Table 1, each member such as a separator, a spacer, and a spring was used to produce a 2032 type coin cell type lithium ion secondary battery.
＜初期放電容量及び容量維持率の測定＞
室温にて、正極に対して１．５ｍＡ／ｃｍ２で４．３Ｖまで充電した後、２．７Ｖまで０．６ｍＡ／ｃｍ２で放電させる充放電を１サイクル行い、初期放電容量を測定した。結果を表２に示す。
次いで、上記放電容量の測定における充放電を１００サイクル行い、下記式により容量維持率を算出した。結果を表２に示す。
容量維持率（％）＝｛（１００サイクル目の放電容量／１サイクル目の放電容量）｝×１００
<Measurement of initial discharge capacity and capacity maintenance ratio>
At room temperature was charged to 4.3V at 1.5 mA / cm 2 to the cathode, performs one cycle of charge and discharge to be discharged at 0.6 mA / cm 2 to 2.7V, was measured and the initial discharge capacity. The results are shown in Table 2.
Next, 100 cycles of charge / discharge in the measurement of the discharge capacity were performed, and the capacity retention rate was calculated by the following formula. The results are shown in Table 2.
Capacity maintenance rate (%) = {(discharge capacity at the 100th cycle / discharge capacity at the first cycle)} × 100
（実施例９、比較例３）
正極にＬｉ金属を用い、表３に示す負極板及び電解液を用いて、セパレータ、スペーサー、バネ等の各部材を使用して、２０３２タイプコインセル型リチウムイオン二次電池を製作した。作製した電池を用い、１．５ｍＡ／ｃｍ２で１．０Ｖまで充電した後（負極板の活物質にＬｉイオン挿入）、２．０Ｖまで０．５ｍＡ／ｃｍ２で放電させる充放電を１サイクル行い、初期放電容量を測定した。結果を表３に示す。
次いで、上記放電容量の測定における充放電を１００サイクル行い、下記式により容量維持率を算出した。結果を表３に示す。
容量維持率（％）＝｛（１００サイクル目の放電容量／１サイクル目の放電容量）｝×１００
(Example 9, Comparative Example 3)
A 2032 type coin cell type lithium ion secondary battery was manufactured using Li metal for the positive electrode, using the negative electrode plate and the electrolyte shown in Table 3, and using each member such as a separator, a spacer, and a spring. Using the produced battery, 1.5 mA / cm 2 after charged to 1.0 V (Li-ion insertion into the active material of the negative electrode plate), charged and discharged 1 cycle to discharge at 0.5 mA / cm 2 to 2.0V The initial discharge capacity was measured. The results are shown in Table 3.
Next, 100 cycles of charge / discharge in the measurement of the discharge capacity were performed, and the capacity retention rate was calculated by the following formula. The results are shown in Table 3.
Capacity maintenance rate (%) = {(discharge capacity at the 100th cycle / discharge capacity at the first cycle)} × 100
＜負荷試験＞
（実施例１０、比較例４）
実施例６及び比較例１と同様にして作製したコインセルを用いて、室温にて正極に対して１．５ｍＡ/ｃｍ２で４．２Ｖまで充電した後、２．７Ｖまで０．６ｍＡ／ｃｍ２で放電させる充放電を１サイクル行い、その初期放電容量を基準として、０．２Ｃ、０．５Ｃ、１．０Ｃ、２．０Ｃ、３．０Ｃの放電電流を計算した。次いで室温にて正極に対して１．５ｍＡ／ｃｍ２で４．２Ｖまで充電した後、０．２Ｃの放電電流で２．７Ｖまで放電させる充放電を３サイクル行って平均値を０．２Ｃ放電時の放電容量とした。０．５Ｃ〜３．０Ｃについても同様に測定を行い、０．２Ｃ放電時の放電容量に対する比を測定した。結果を図１に示す。その結果、本発明に係る表面処理を行うことによって負荷特性が向上していることが分かる。
<Load test>
(Example 10, comparative example 4)
Using the coin cells were prepared in the same manner as in Example 6 and Comparative Example 1 was charged to 4.2V at 1.5 mA / cm 2 to the cathode at room temperature, 0.6 mA / cm 2 until 2.7V 1 cycle of charge / discharge was performed, and discharge currents of 0.2C, 0.5C, 1.0C, 2.0C, and 3.0C were calculated based on the initial discharge capacity. Next, after charging to 4.2 V at 1.5 mA / cm 2 with respect to the positive electrode at room temperature, 3 cycles of charge / discharge were performed to discharge to 2.7 V with a discharge current of 0.2 C, and the average value was 0.2 C discharge. The discharge capacity at the time. The same measurement was performed for 0.5C to 3.0C, and the ratio to the discharge capacity at the time of 0.2C discharge was measured. The results are shown in FIG. As a result, it is understood that the load characteristics are improved by performing the surface treatment according to the present invention.
＜正極活物質と電解液の示差走査熱量測定（Differential Scanning Calorimetry, DSC）＞
（実施例１１〜１２、比較例５〜６）
実施例６、７及び比較例１、２と同様に作製したリチウム二次電池をそれぞれ室温（２５℃）にて正極に対して１．５ｍＡ／ｃｍ２で４．２Ｖまで充電した後、電池を分解し、充電状態の正極を取り出してジメチルカーボネートで洗浄した。この正極を乾燥させた後削り取り、ＳＵＳ製密封型ＤＳＣ測定セルに電極５ｍｇと電池作製時に使用した電解液と同じ電解液５μＬを封入した。この測定セルをＤＳＣ測定装置（セイコーインスツルメンタル社製、ＤＳＣ６２００）で昇温速度２℃／ｍｉｎ．にて１５０〜３００℃の範囲でＤＳＣ測定を行った。１５０〜３００℃の範囲での電極と電解液の重量あたりの発熱量を表４に、ＤＳＣ測定結果をそれぞれ図２、図３、図４及び図５に示す。
<Differential Scanning Calorimetry (DSC)>
(Examples 11-12, Comparative Examples 5-6)
The lithium secondary batteries produced in the same manner as in Examples 6 and 7 and Comparative Examples 1 and 2 were charged to 4.2 V at 1.5 mA / cm 2 with respect to the positive electrode at room temperature (25 ° C.), respectively. After decomposition, the charged positive electrode was taken out and washed with dimethyl carbonate. The positive electrode was dried and then scraped off, and 5 mg of the electrode and 5 μL of the same electrolyte as the electrolyte used for battery production were sealed in a sealed DSC measurement cell made of SUS. This measurement cell was measured with a DSC measuring apparatus (DSC6200, manufactured by Seiko Instrumental Co., Ltd.) at a temperature rising rate of 2 ° C./min. DSC measurement was performed in the range of 150 to 300 ° C. Table 4 shows the calorific value per weight of the electrode and the electrolyte in the range of 150 to 300 ° C., and DSC measurement results are shown in FIG. 2, FIG. 3, FIG. 4 and FIG.
Claims (17)
Ｍ１ （ａ）Ｘ（ｂ） （１）
（式中、Ｍ１は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ａｌ、Ｇｅ、Ｔｉ及びＺｒのうちの１種又は２種以上の多価のカチオンである。Ｘは、リチウムイオン二次電池の電解質用リチウム塩のアニオンである。ａ＞０であり、ｂ＞０である。）
で表わされる化合物であることを特徴とするリチウム系複合酸化物の表面処理剤。 The following general formula (1):
M 1 (a) X (b) (1)
(In the formula, M 1 is one or more polyvalent cations of Mg, Ca, Sr, Ba, Zn, Al, Ge, Ti, and Zr. X is a lithium ion secondary battery. An anion of the lithium salt for electrolytes, a> 0 and b> 0.)
A surface treatment agent for a lithium-based composite oxide, which is a compound represented by the formula:
Ｌｉ（ｃ）Ｎｉ（ｄ）Ｃｏ（ｅ）Ｍｎ（ｆ）Ａｌ（ｇ）Ｏ２ （３）
（式中、０．８≦ｃ≦１．２、０≦ｄ≦１、０≦ｅ≦１、０≦ｆ≦１、０≦ｇ≦０．１、ｄ＋ｅ＋ｆ＋ｇ＝１である。）
で表わされるリチウム系複合酸化物であることを特徴とする請求項７記載の表面処理リチウムイオン二次電池用正極活物質。 The lithium-based composite oxide for the positive electrode active material of the lithium ion secondary battery has the following general formula (3):
Li (c) Ni (d) Co (e) Mn (f) Al (g) O 2 (3)
(In the formula, 0.8 ≦ c ≦ 1.2, 0 ≦ d ≦ 1, 0 ≦ e ≦ 1, 0 ≦ f ≦ 1, 0 ≦ g ≦ 0.1, d + e + f + g = 1)
The positive electrode active material for a surface-treated lithium ion secondary battery according to claim 7, wherein the lithium-based composite oxide is represented by the formula:
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